EP1606041B1 - Procede d elimination selective de sulfure d hydrogene et de co 2 dans des gaz bruts - Google Patents

Procede d elimination selective de sulfure d hydrogene et de co 2 dans des gaz bruts Download PDF

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Publication number
EP1606041B1
EP1606041B1 EP04722813A EP04722813A EP1606041B1 EP 1606041 B1 EP1606041 B1 EP 1606041B1 EP 04722813 A EP04722813 A EP 04722813A EP 04722813 A EP04722813 A EP 04722813A EP 1606041 B1 EP1606041 B1 EP 1606041B1
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EP
European Patent Office
Prior art keywords
stage
absorption
gas
flash
desorption
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
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EP04722813A
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German (de)
English (en)
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EP1606041A2 (fr
Inventor
Johannes Menzel
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ThyssenKrupp Industrial Solutions AG
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Uhde GmbH
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
    • C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
    • C10L3/10—Working-up natural gas or synthetic natural gas
    • C10L3/101—Removal of contaminants
    • C10L3/102—Removal of contaminants of acid contaminants
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
    • B01D53/1406—Multiple stage absorption
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
    • B01D53/1425—Regeneration of liquid absorbents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
    • B01D53/1456—Removing acid components
    • B01D53/1462—Removing mixtures of hydrogen sulfide and carbon dioxide
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
    • C01B3/52—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by contacting with liquids; Regeneration of used liquids
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
    • C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
    • C10L3/10—Working-up natural gas or synthetic natural gas
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/0415—Purification by absorption in liquids
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/0465—Composition of the impurity
    • C01B2203/0485—Composition of the impurity the impurity being a sulfur compound
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/151—Reduction of greenhouse gas [GHG] emissions, e.g. CO2

Definitions

  • the invention is directed to a method for the selective removal of hydrogen sulfide, organic sulfur components and CO 2 from raw natural gas of the type specified in the preamble of claim 1, as for example in the U.S. 5,820,837-A is described.
  • Recyclable gases such as natural gas or synthesis gas
  • acid-forming impurities such as CO 2 , H 2 S, COS, CS 2 and / or mercaptans and HCN, which must be removed because of the further use of the gases.
  • Legal regulations force not only the reduction of sulfur emissions, but also the CO 2 components, which also lower the calorific value. Impurities can be annoying catalyst poisons, cause corrosion u. like. More.
  • chemical absorbents such as ethanolamine, alkali salt solutions, etc.
  • physical absorbents such as selexol, propylene carbonate, methanol, among others, which can also be removed by physical absorption of organic sulfur components.
  • a selective absorbent By choice and use of a selective absorbent can be quite a good selectivity of the removal of hydrogen sulfide and organic sulfur compounds with respect to carbon dioxide already achieved.
  • a selective absorbent both chemically acting absorbents, such as selective amines, as well as physical absorbents, such as Selexol, Pursiol, Genosorb or Morphysorb used.
  • this selectivity is sufficient not when a particularly unfavorable ratio of hydrogen sulfide and organic sulfur compounds to carbon dioxide in the feed gas leads to an acid gas with such a low content of sulfur components that the sour gas can no longer be processed in a Claus plant.
  • the present invention is directed in particular to chemically non-active absorbent on the one hand to recover as pure CO 2 as valuable material, and on the other with sour gas or gas for use in a Claus process with the required there To gain quality characteristics.
  • the sour gas coming from the absorption medium regeneration is further processed to sulfur in a Claus plant.
  • the carbon dioxide contained in the sour gas has an adverse effect on this Claus process, since carbon dioxide as fiber increases the process gas flow in the Claus plant, which makes a corresponding increase in investment capacity necessary.
  • a Claus plant with an acid gas containing less than 10 vol .-% of H 2 S technically no longer operate economically.
  • the concentration of the sulfur components is characterized in that the sulfur components contained in the low-concentration sour gas are removed by means of a second absorption column after any additional compression with regenerated absorption solution again, due to the already better ratios of hydrogen sulfide and organic sulfur compounds in relation on carbon dioxide in the sour gas from the first absorption stage, a correspondingly higher concentration of sulfur components in the sour gas of the second absorption stage is achieved.
  • this approach is very energy and investment costs consuming, since the entire sour gas stream from the first absorption stage must first be brought to the necessary absorption pressure.
  • the absorbent is expanded into a flash vessel at reduced pressure.
  • the resulting gas phase is fed back to the second absorption column by means of a flash gas compressor.
  • a flash stage is arranged directly in front of the second absorption stage, in which the absorbent coming from the condensation stage is expanded and the released value gas, which contains substantially hydrocarbons, H 2 S and CO 2 , is returned to the first absorption stage.
  • the absorption to take place at an operating pressure of 10 to 150 bar and / or a temperature increase of the enriched absorbent coming from the absorber to 50 to 200 ° C.
  • Contains the main stream of the absorbent leaving the high-pressure flash tank still too high amount of carbon dioxide may be provided in a further embodiment of the invention that the high-pressure flash tank leaving enriched absorption solution is expanded in a low-pressure flash, wherein the flash gas by means of a common compressor of second absorption column is supplied together with the flash gas from the flash stage and wherein the low-pressure flash leaving the absorption solution is fed to the head of the desorption.
  • the flash gas of the low pressure flash tank is cooled by a chiller before the flash gas is fed to the flash gas compressor.
  • the almost pure carbon dioxide recovered at the top of the second absorption column at elevated pressure can either be re-used in the process or obtained as a salable product or used for the purpose of re-injection into natural gas and oil fields due to the already increased form.
  • the increased pressure level can be used by an expander machine for energy recovery.
  • the desired concentration of the sulfur components in the sour gas can be further adjusted via the pressure of the low-pressure flash stage, for most applications, an advantageous pressure between 3 to 10 bar results, which in the recompression of low-pressure flash gases to further significant savings in operating and Investment costs compared to a conventional two-stage absorption leads.
  • the plant shown initially has a first designated 41 absorption column, shown in the diagram on the left, on, which is fed with the natural gas or synthesis gas via the line 1, which flows through the absorption column from bottom to top and above the line 2 as cleaned gas leaves.
  • the feed gas 1 is fed to the bottom of the absorption column 41.
  • the sour gas components contained in the gas are removed in countercurrent from the regenerated solution 14 charged in the top of the absorption column 41, the mass transfer elements contained in the absorption column 41 providing the necessary mass transfer.
  • Table 2 Calculated counterexample of a typical absorber / desorber circuit according to Fig. 2 , Gas flow rate H 2 S CO 2 Temp Pres Absorbent flow Current no. kmol / h kmol / h kmol / h ° C bar m 3 / h 1 10000.0 100.0 3571.7 40 61 - 2 9129.3 0.0130 2829.8 -1 60.2 - 9 870.7 100.0 741.9 12.6 1.4 - 5 - 100.0 741.9 7.3 60.4 199 11 - 0001 0.0 142.7 67 156

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Analytical Chemistry (AREA)
  • Combustion & Propulsion (AREA)
  • Inorganic Chemistry (AREA)
  • Gas Separation By Absorption (AREA)
  • Treating Waste Gases (AREA)
  • Exhaust Gas Treatment By Means Of Catalyst (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Hydrogen, Water And Hydrids (AREA)

Claims (6)

  1. Procédé pour l'élimination sélective de sulfure d'hydrogène, de composants organiques soufrés et de CO2 à partir de gaz bruts, tels que par exemple le gaz naturel ou le gaz de synthèse, utilisant une première étape d'absorption (41) et une seconde étape d'absorption (49) pour la séparation de CO2 sensiblement pur et utilisant une étape de désorption (50) pour l'obtention d'un gaz enrichi en sulfure d'hydrogène, dans lequel l'agent absorbant régénéré provenant de l'étape de désorption (50) est recyclé vers les deux étapes d'absorption (41, 49), l'agent absorbant étant un solvant chimiquement inerte, et
    dans lequel l'agent absorbant provenant de la première étape d'absorption (41) (contenant du sulfure d'hydrogène, des composés organiques soufrés et enrichi en CO2) est préchauffé, avec la solution régénérée chaude (12) provenant de l'étape de désorption (50), dans un échangeur de chaleur (44), et ensuite détendu dans un récipient d'évaporation éclair haute pression (47) puis amené vers la seconde étape d'absorption (49), et
    dans lequel l'agent absorbant provenant de la seconde étape d'absorption (49) est recyclé (26/27) vers l'étape de désorption (50),
    caractérisé en ce que
    - l'agent absorbant, provenant de l'étape d'absorption (41), est détendu à une pression élevée, intermédiaire entre la pression de la colonne d'absorption (41) et la pression de la colonne de désorption (50), à la pression supérieure choisie dans le récipient d'évaporation éclair haute pression (47),
    - le flux gazeux libéré à pression élevée est refroidi dans un condensateur (48) et est ensuite amené vers la seconde étape d'absorption (49) dans laquelle les composants soufrés sont entièrement éliminés au moyen du flux partiel (mentionné ci-avant) d'agent absorbant (15, 16, 17) régénéré provenant de l'étape de désorption (50), et
    - après la seconde étape d'absorption (49), il est prévu une étape d'évaporation éclair (55) dans laquelle l'agent absorbant chargé, provenant de la seconde étape d'absorption, est détendu, et le gaz d'évaporation éclair (19) libéré, qui contient essentiellement du CO2 et des fractions de H2S, est amené dans une conduite menant au moins indirectement à la seconde étape d'absorption et l'agent absorbant (26) est amené vers l'étape de désorption.
  2. Procédé selon la revendication 1, caractérisé en ce que l'agent absorbant chargé (18) est chauffé, après la seconde étape d'absorption (49) et avant l'entrée dans l'étape de désorption, le réchauffage s'effectuant par échange de chaleur indirect (52), avec le flux d'agent absorbant (15) provenant de l'étape de désorption.
  3. Procédé selon la revendication 1 ou 2, caractérisé en ce qu'une étape d'évaporation éclair (55) est prévue directement en amont de la seconde étape d'absorption (49), étape dans laquelle l'agent absorbant (9) provenant de l'étape de condensation (48) est détendu et le gaz libéré, contenant essentiellement des hydrocarbures, du H2S et du CO2, est recyclé vers la première étape d'absorption (41).
  4. Procédé selon la revendication 1 ou 2 à 3, caractérisé en ce que l'absorption s'effectue à une pression de fonctionnement de 10 à 150 bars.
  5. Procédé selon la revendication 1 ou 3 à 4, caractérisé en ce qu'on augmente la température de l'agent absorbant enrichi, provenant de l'absorbeur, jusqu'à 50 - 200°C.
  6. Procédé selon la revendication 1, caractérisé en ce que la solution d'absorption enrichie quittant le récipient d'évaporation éclair à haute pression (47) est détendue dans un récipient d'évaporation éclair basse pression (56), le gaz d'évaporation éclair étant amené au moyen d'un condensateur commun (58) vers la deuxième colonne d'absorption (49), conjointement avec le gaz d'évaporation éclair provenant de l'étape d'évaporation éclair (55) et la solution d'absorption quittant le récipient d'évaporation éclair basse pression (56) est alors amenée jusqu'à la tête de la colonne de désorption.
EP04722813A 2003-03-26 2004-03-24 Procede d elimination selective de sulfure d hydrogene et de co 2 dans des gaz bruts Expired - Lifetime EP1606041B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10313438A DE10313438A1 (de) 2003-03-26 2003-03-26 Verfahren zur selektiven Entfernung von Schwefelwasserstoff und CO2 aus Rohgas
DE10313438 2003-03-26
PCT/EP2004/003085 WO2004085036A2 (fr) 2003-03-26 2004-03-24 Procede d'elimination selective de sulfure d'hydrogene et de co2 dans des gaz bruts

Publications (2)

Publication Number Publication Date
EP1606041A2 EP1606041A2 (fr) 2005-12-21
EP1606041B1 true EP1606041B1 (fr) 2008-04-23

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Country Status (9)

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US (1) US7604684B2 (fr)
EP (1) EP1606041B1 (fr)
CN (1) CN100406106C (fr)
AT (1) ATE392939T1 (fr)
CA (1) CA2532993C (fr)
DE (2) DE10313438A1 (fr)
ES (1) ES2303631T3 (fr)
NO (1) NO329963B1 (fr)
WO (1) WO2004085036A2 (fr)

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WO2013013749A1 (fr) 2011-07-28 2013-01-31 Thyssenkrupp Uhde Gmbh Récupération de chaleur au cours de processus d'absorption et de désorption

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DE4121436A1 (de) 1991-06-28 1993-01-07 Linde Ag Verfahren zur selektiven h(pfeil abwaerts)2(pfeil abwaerts)s-auswaschung
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CA2177449C (fr) * 1996-05-20 2003-04-29 Barry Steve Marjanovich Methode de traitement d'un circuit gazeux pour en separer selectivement les gaz acides
DE19854353A1 (de) * 1998-11-25 2000-06-21 Clariant Gmbh Verfahren zur Reinigung von Gasen
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DE19945326B4 (de) * 1999-01-22 2008-03-27 Uhde Gmbh Verfahren zur Entfernung von Kohlendioxid, Schwefelverbindungen, Wasser und aromatischen und höheren aliphatischen Kohlenwasserstoffen aus technischen Gasen
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DE102010051396A1 (de) 2010-11-16 2012-05-16 Thyssenkrupp Uhde Gmbh Verfahren zur Entfernung schwersiedender Kohlenwasserstoffe aus Lösungsmittelströmen
WO2012065703A1 (fr) 2010-11-16 2012-05-24 Thyssenkrupp Uhde Gmbh Procédé pour l'élimination d'hydrocarbures à point d'ébullition élevé de courants de solvants
WO2013013750A1 (fr) 2011-07-25 2013-01-31 Thyssenkrupp Uhde Gmbh Récupération de chaleur au cours de processus d'absorption et de désorption avec une surface d'échange thermique réduite
DE102011108308A1 (de) 2011-07-25 2013-01-31 Thyssenkrupp Uhde Gmbh Wärmerückgewinnung bei Absorptions- und Desorptionsprozessen bei reduzierter Wärmeaustauschfläche
WO2013013749A1 (fr) 2011-07-28 2013-01-31 Thyssenkrupp Uhde Gmbh Récupération de chaleur au cours de processus d'absorption et de désorption
DE102011108749A1 (de) 2011-07-28 2013-01-31 Thyssenkrupp Uhde Gmbh Wärmerückgewinnung bei Absorptions- und Desorptionsprozessen

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CA2532993A1 (fr) 2004-10-07
ATE392939T1 (de) 2008-05-15
NO329963B1 (no) 2011-01-31
CA2532993C (fr) 2012-07-17
ES2303631T3 (es) 2008-08-16
WO2004085036A3 (fr) 2004-11-25
CN1795039A (zh) 2006-06-28
WO2004085036A2 (fr) 2004-10-07
US20060196357A1 (en) 2006-09-07
NO20054940D0 (no) 2005-10-25
DE10313438A1 (de) 2004-11-04
US7604684B2 (en) 2009-10-20
DE502004006914D1 (de) 2008-06-05
CN100406106C (zh) 2008-07-30
NO20054940L (no) 2005-12-21
EP1606041A2 (fr) 2005-12-21

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